CN106715539A - Modified solid polyalkylaluminoxane and catalyst for olefin oligomerization reaction - Google Patents

Abstract

The object of the present invention is to provide a modified solid capable of producing α-olefins while suppressing the adhesion of polymers produced by side reactions to the walls of reactors and mixers, and to provide highly active catalysts for olefin oligomerization reactions shape polyalkylaluminoxane; and a catalyst for olefin oligomerization containing the modified solid polyalkylaluminoxane. The present invention relates to a modified solid polyalkylaluminoxane used in olefin oligomerization reaction, which has a median diameter of 0.1 μm or more and 50 μm or less, and has a structural unit represented by the following general formula (a), and Describe the structural unit represented by the general formula (b).

Description

Catalyst for oligomerization reaction of modified solid polyalkylaluminoxane and olefin

technical field

This patent application claims Japanese Patent Application No. 2014-199907 (application date: September 30, 2014) and Japanese Patent Application No. 2015-083980 (application date: April 16, 2015) based on the Paris Convention priority, It is hereby incorporated by reference into this specification in its entirety.

The present invention relates to a catalyst for the oligomerization reaction between a modified solid polyalkylaluminoxane and an olefin. The modified solid polyalkylaluminoxane can suppress the adhesion of polymers produced by side reactions to the wall of the reactor, Simultaneously producing α-olefins on a mixer, and capable of giving a highly active olefin oligomerization catalyst containing the modified solid polyalkylaluminoxane.

Background technique

α-Olefin is a compound widely used industrially as a raw material of polyolefin. The olefin oligomerization reaction is a reaction capable of producing α-olefins, and in recent years, development of catalysts for olefin oligomerization reactions capable of producing α-olefins with high selectivity has been carried out (Patent Documents 1 to 5).

prior art literature

patent documents

Patent Document 1: U.S. Patent No. 5,856,257

Patent Document 2: Japanese Patent Laid-Open No. 2011-98954

Patent Document 3: Japanese Patent Laid-Open No. 2012-213765

Patent Document 4: WO2009/005003

Patent Document 5: Japanese Patent Laid-Open No. 2011-178682.

Contents of the invention

The problem to be solved by the invention

However, the activity of the catalysts described in the above patent documents is not necessarily satisfactory. In addition, when α-olefins are produced by olefin oligomerization using the catalysts described in the above-mentioned patent documents, polymers produced by side reactions adhere to the walls of reactors, mixers, etc., making it difficult to perform long-term operation.

Based on the above circumstances, the problem to be solved by the present invention is to provide an olefin oligomerization system capable of producing α-olefins while suppressing the adhesion of polymer produced by side reactions to the wall of the reactor and the mixer, and giving high activity. A modified solid polyalkylaluminoxane catalyst for reaction; and a catalyst for olefin oligomerization containing the modified solid polyalkylaluminoxane.

method used to solve the problem

The present invention relates to a modified solid polyalkylaluminoxane used in olefin oligomerization reaction, which has a median diameter of 0.1 μm or more and 50 μm or less, and has a structural unit represented by the following general formula (a), and Describe the structural unit represented by the general formula (b).

[R' in general formula (a) is an alkyl group with 1 to 20 carbon atoms, and R'' in general formula (b) is a halogenated alkoxy group with 1 to 20 carbon atoms, or a halogenated aryloxy group having 6 to 20 carbon atoms].

Invention effect

According to the present invention, it is possible to provide a modified solid-state catalyst for olefin oligomerization that can produce α-olefins while suppressing the adhesion of polymers produced by side reactions to the walls of reactors and mixers, and can provide high activity. a polyalkylaluminoxane; and a catalyst for olefin oligomerization containing the modified solid polyalkylaluminoxane.

detailed description

The modified solid polyalkylaluminoxane of the present invention is a modified solid polyalkylaluminoxane used in olefin oligomerization reactions, has a median diameter of 0.1 μm or more and 50 μm or less, and has the following general formula A structural unit represented by (a), and a structural unit represented by the following general formula (b). In the modified solid polyalkylaluminoxane, the structural unit represented by the following general formula (a) and the structural unit represented by the following general formula (b) may be connected in a ring or in a chain, A mixture of them is also possible. In addition, in the modified solid polyalkylaluminoxane, a structural unit represented by the following general formula (a) and a structural unit represented by the following general formula (b) may be bonded in random order.

.

R' in the general formula (a) is an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms in R' include methyl, ethyl, n-propyl, cyclopropyl, isopropyl, n-butyl, isobutyl, and sec-butyl. , tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropane base, 1,2-dimethylpropyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl. It is preferably methyl, ethyl, isobutyl, hexyl, or octyl, more preferably methyl, ethyl, or isobutyl, and still more preferably methyl, or isobutyl.

R'' in the general formula (b) is a halogenated alkoxy group having 1 to 20 carbon atoms, or a halogenated aryloxy group having 6 to 20 carbon atoms.

Examples of the haloalkoxy group having 1 to 20 carbon atoms in R'' include fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, difluoromethoxy, Chloromethoxy, dibromomethoxy, diiodomethoxy, trifluoromethoxy, trichloromethoxy, tribromomethoxy, triiodomethoxy, 2,2,2-trifluoroethane Oxygen, 2,2,2-trichloroethoxy, 2,2,2-tribromoethoxy, 2,2,2-triiodoethoxy, 2,2,3,3,3-penta Fluoropropoxy, 2,2,3,3,3-pentachloropropoxy, 2,2,3,3,3-pentabromopropoxy, 2,2,3,3,3-pentaiodopropoxy Oxygen, 2,2,2-trifluoro-1-(trifluoromethyl)ethoxy, 2,2,2-trichloro-1-(trichloromethyl)ethoxy, 2,2,2 -Tribromo-1-(tribromomethyl)ethoxy, 2,2,2-triiodo-1-(triiodomethyl)ethoxy, 1,1-bis(trifluoromethyl)-2 ,2,2-trifluoroethoxy, 1,1-bis(trichloromethyl)-2,2,2-trichloroethoxy, 1,1-bis(tribromomethyl)-2,2 , 2-tribromoethoxy, 1,1-bis(triiodomethyl)-2,2,2-triiodoethoxy, perfluoro-n-butoxy, etc.

Examples of the halogenated aryloxy group having 6 to 20 carbon atoms in R'' include 2-fluorophenoxy, 3-fluorophenoxy, 4-fluorophenoxy, 2,4- Difluorophenoxy, 2,6-difluorophenoxy, 3,4-difluorophenoxy, 3,5-difluorophenoxy, 2,4,6-trifluorophenoxy, 3, 4,5-Trifluorophenoxy, 2,3,5,6-tetrafluorophenoxy, pentafluorophenoxy, 2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzene Oxygen, 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenoxy, perfluoro-1-naphthyloxy, perfluoro-2-naphthyloxy, 2-chlorophenoxy , 3-chlorophenoxy, 4-chlorophenoxy, 2,4-dichlorophenoxy, 2,6-dichlorophenoxy, 3,4-dichlorophenoxy, 3,5-dichlorophenoxy Chlorophenoxy, 2,4,6-trichlorophenoxy, 3,4,5-trichlorophenoxy, 2,3,5,6-tetrachlorophenoxy, pentachlorophenoxy, 2 ,3,5,6-tetrachloro-4-(trichloromethyl)phenoxy, 2,3,5,6-tetrachloro-4-(pentachlorophenyl)phenoxy, perchloro-1- Naphthyloxy, perchloro-2-naphthyloxy, 2-bromophenoxy, 3-bromophenoxy, 4-bromophenoxy, 2,4-dibromophenoxy, 2,6-dibromo Phenoxy, 3,4-dibromophenoxy, 3,5-dibromophenoxy, 2,4,6-tribromophenoxy, 3,4,5-tribromophenoxy, 2, 3,5,6-tetrabromophenoxy, pentabromophenoxy, 2,3,5,6-tetrabromo-4-(tribromomethyl)phenoxy, 2,3,5,6-tetrabromophenoxy Bromo-4-(pentabromophenyl)phenoxy, perbromo-1-naphthyloxy, perbromo-2-naphthyloxy, 2-iodophenoxy, 3-iodophenoxy, 4-iodobenzene Oxygen, 2,4-diiodophenoxy, 2,6-diiodophenoxy, 3,4-diiodophenoxy, 3,5-diiodophenoxy, 2,4,6-tri Iodophenoxy, 3,4,5-triiodophenoxy, 2,3,5,6-tetraiodophenoxy, pentaiodophenoxy, 2,3,5,6-tetraiodo-4- (Triiodomethyl)phenoxy, 2,3,5,6-tetraiodo-4-(pentaiodophenyl)phenoxy, periodo-1-naphthyloxy, periodo-2-naphthyloxy , 2-(trifluoromethyl)phenoxy, 3-(trifluoromethyl)phenoxy, 4-(trifluoromethyl)phenoxy, 2,6-bis(trifluoromethyl)phenoxy 3,5-bis(trifluoromethyl)phenoxy, 2,4,6-tri(trifluoromethyl)phenoxy, 3,4,5-tri(trifluoromethyl)phenoxy Wait.

R'' is preferably a halogenated aryloxy group, more preferably a fluoroaryloxy group, further preferably 2,4,6-trifluorophenoxy, 3,4,5-trifluorophenoxy, pentafluorophenoxy, Fluorophenoxy, 2,6-bis(trifluoromethyl)phenoxy, 3,5-(bistrifluoromethyl)phenoxy, or 2,4,6-tris(trifluoromethyl)benzene An oxy group is still more preferably a pentafluorophenoxy group.

The unit number (m) of the structural unit represented by the general formula (b) in the modified solid polyalkylaluminoxane is the same as the unit number (n) of the structural unit represented by the general formula (a) and the general formula ( The ratio (m/(m+n)) of the total number of units (m) of the structural units shown in b) is preferably 0.05 or more and 0.5 or less.

Regarding the ratio (m/(m+n)), elemental analysis was performed on the modified solid polyalkylaluminoxane, and the obtained modified solid polyalkylaluminoxane was composed of aluminum atoms, fluorine atoms, carbon atoms, Calculated from the ratio of oxygen atoms and hydrogen atoms.

Known methods such as ICP emission analysis and EPMA analysis can be mentioned as the method of the above-mentioned elemental analysis.

The modified solid polyalkylaluminoxane is in the form of particles, and has a median diameter of preferably 0.1 μm to 50 μm, more preferably 1 μm to 30 μm. Furthermore, the particle size distribution is preferably narrow. The median diameter and particle size distribution of the modified solid polyalkylaluminoxane can be determined by a laser diffraction/scattering method in a dry hydrocarbon solvent using a laser diffraction particle size distribution measuring device.

The particle size distribution is expressed by the Span value, and the smaller the Span value, the narrower the particle size distribution. The Span value is more preferably 2 or less. The Span value can be obtained by laser diffraction particle size distribution measurement using the values of particle diameter D10 with a cumulative distribution of 10%, D50 (median diameter) with a cumulative distribution of 50%, and D90 with a cumulative distribution of 90%. formula to find out.

Span value = (D90-D10)/D50.

For the modified solid polyalkylaluminoxane of the present invention, in the equilibrium state in n-hexane or toluene at 25°C, the number of moles of the aluminum compound dissolved in the solvent relative to the modified solid polyalkylaluminum The ratio of the number of moles of aluminum in oxane is preferably not less than 0 mol % and not more than 2 mol %.

The modified solid polyalkylaluminoxane can be obtained by mixing the solid polyalkylaluminoxane with a halogenated alcohol having 1 to 20 carbon atoms or a halogenated phenol having 6 to 20 carbon atoms. obtained by a reaction. "Phenols" in halogenated phenols is a general term for compounds having a hydroxyl group on an aromatic ring.

The content of aluminum atoms contained in the solid polyalkylaluminoxane is preferably 36% by weight or more and 43% by weight or less. However, the total amount of solid polyalkylaluminoxane is defined as 100% by weight. The content of aluminum atoms in the solid polyalkylaluminoxane can be determined by known means, for example, the means described in International Publication No. 2010/055652.

The solid polyalkylaluminoxane preferably has a median diameter of 50 μm or less and a narrow particle size distribution. The median diameter and particle size distribution can be obtained by a laser diffraction particle size distribution measuring device similarly to the modified solid polyalkylaluminoxane, and the Span value, which is an index of the particle size distribution, is preferably 2 or less.

Examples of the solid polyalkylaluminoxane include solid polymethylaluminoxane, solid polymethylisobutylaluminoxane, solid polyisobutylaluminoxane, and the like, preferably solid polyalkylaluminoxane. Methylaluminoxane.

Examples of methods for producing solid polyalkylaluminoxane include heating and reducing the pressure of an aromatic hydrocarbon solution containing polyalkylaluminoxane and trialkylaluminum to remove the aromatic hydrocarbon solvent and trialkylaluminum. , making it dry, thereby obtaining a solid polyalkylaluminoxane method; adding an aromatic hydrocarbon solution containing polyalkylaluminoxane and trialkylaluminum to an aliphatic hydrocarbon solvent, thereby making a solid state A method of precipitating a polyalkylaluminoxane; a method of precipitating a solid polyalkylaluminoxane by heating an aromatic hydrocarbon mixture containing a polyalkylaluminoxane and a trialkylaluminum; and the like. More preferably, it is a method of heating an aromatic hydrocarbon solution of polyalkylaluminoxane and trialkylaluminum, the heating temperature is preferably 80°C to 200°C, and the heating time is preferably 5 minutes to 24 hours.

Examples of methods for producing polyalkylaluminoxane include: a method of reacting an alkylaluminum with water; reacting an oxygen-containing organic compound with a trialkylaluminum to obtain an alkyl group having an aluminum-oxygen-carbon bond; Aluminum compound, and the method for thermally decomposing the obtained alkylaluminum compound. A method of thermally decomposing a compound obtained by reacting an oxygen-containing organic compound with a trialkylaluminum is preferred. As the oxygen-containing organic compound, a carboxylic acid is preferable.

Examples of the halogen in the halogenated alcohols having 1 to 20 carbon atoms or the halogenated phenols having 1 to 20 carbon atoms include fluorine, chlorine, bromine or iodine.

Examples of halogenated alcohols having 1 to 20 carbon atoms include fluoromethanol, difluoromethanol, trifluoromethanol, chloromethanol, dichloromethanol, trichloromethanol, bromomethanol, dibromomethanol, and tribromomethanol. , iodomethanol, diiodomethanol, triiodomethanol, fluoroethanol, difluoroethanol, trifluoroethanol, tetrafluoroethanol, pentafluoroethanol, chloroethanol, dichloroethanol, trichloroethanol, tetrachloroethanol, pentachloroethanol, Bromoethanol, dibromoethanol, tribromoethanol, tetrabromoethanol, pentabromoethanol, perfluoro-1-propanol, perfluoro-2-propanol, perfluoro-1-butanol, perfluoro-2-methyl -1-propanol, perfluoro-2-butanol, perfluoro-2-methyl-2-propanol, perfluoro-1-pentanol, perfluoro-1-hexanol, perfluoro-1-octanol , perfluoro-1-dodecanol, perfluoro-1-pentadecanol, perfluoro-1-eicosanol, perchloro-1-propanol, perchloro-2-propanol, perchloro- 1-butanol, perchloro-2-methyl-1-propanol, perchloro-2-butanol, perchloro-2-methyl-2-propanol, perchloro-1-pentanol, perchloro- 1-Hexanol, Perchloro-1-octanol, Perchloro-1-Dodecanol, Perchloro-1-Pentadecanol, Perchloro-1-Eicosanol, Perbromo-1-Propanol , Perbromo-2-propanol, Perbromo-1-butanol, Perbromo-2-methyl-1-propanol, Perbromo-2-butanol, Perbromo-2-methyl-2-propanol , Perbromo-1-pentanol, Perbromo-1-hexanol, Perbromo-1-octanol, Perbromo-1-dodecanol, Perbromo-1-pentadecanol, Perbromo-1- eicosanol, etc. The halogenated alcohol having 1 to 20 carbon atoms is preferably a fluoroalcohol, more preferably trifluoromethanol, perfluoro-2-propanol, or perfluoro-2-methyl-2-propanol.

Examples of halogenated phenols having 6 to 20 carbon atoms include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol Phenol, 2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenol, 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenol, 2,6-bis( Trifluoromethyl)phenol, 3,5-bis(trifluoromethyl)phenol, 2,4,6-tris(trifluoromethyl)phenol, perfluoro-1-naphthol, perfluoro-2-naphthol , 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2, 4,6-Trichlorophenol, 3,4,5-Trichlorophenol, 2,3,5,6-Tetrachlorophenol, Pentachlorophenol, 2,3,5,6-Tetrachloro-4-(Trichlorophenol Methyl)phenol, 2,3,5,6-tetrachloro-4-(pentachlorophenyl)phenol, 2,6-bis(trichloromethyl)phenol, 3,5-bis(trichloromethyl) Phenol, 2,4,6-tris(trichloromethyl)phenol, perchloro-1-naphthol, perchloro-2-naphthol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2, 4-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4,6-tribromophenol, 3,4,5-tribromophenol, 2,3,5,6-tetrabromophenol, pentabromophenol, 2,3,5,6-tetrabromo-4-(tribromomethyl)phenol, 2,3,5,6-tetrabromo-4- (Pentabromophenyl)phenol, 2,6-bis(tribromomethyl)phenol, 3,5-bis(tribromomethyl)phenol, 2,4,6-tris(tribromomethyl)phenol, all Bromo-1-naphthol, perbromo-2-naphthol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4- Diiodophenol, 3,5-diiodophenol, 2,4,6-triiodophenol, 3,4,5-triiodophenol, 2,3,5,6-tetraiodophenol, pentaiodophenol, 2, 3,5,6-tetraiodo-4-(triiodomethyl)phenol, 2,3,5,6-tetraiodo-4-(pentaiodophenyl)phenol, 2,6-bis(triiodomethyl) ) phenol, 3,5-bis(triiodomethyl)phenol, 2,4,6-tris(triiodomethyl)phenol, periodo-1-naphthol, periodo-2-naphthol, etc. The halogenated phenols having 6 to 20 carbon atoms are preferably fluorophenols, more preferably 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 2,6-bis(trifluoromethyl)phenol, 3,5-bis(trifluoromethyl)phenol, or 2,4,6-tris(trifluoromethyl)phenol, more preferably pentafluorophenol.

From the viewpoint of the long-lasting activity of the catalyst for olefin oligomerization reaction and the viewpoint of suppressing the formation of side reactions of the polymer, a halogenated alcohol having 1 to 20 carbon atoms or a halogenated halogen having 6 to 20 carbon atoms The amount of substituted phenols used is preferably 0.01 equivalent to less than 1.0 equivalent, more preferably 0.05 equivalent to less than 1.0 equivalent, and still more preferably 0.1 equivalent to the aluminum atom in the modified solid polyalkylaluminoxane. 0.7 equivalent or more, and more preferably 0.2 equivalent or more and 0.5 equivalent or less.

Preferably, a solid polyalkylaluminoxane is reacted with a halogenated alcohol having 1 to 20 carbon atoms or a halogenated phenol having 6 to 20 carbon atoms in the presence of a solvent.

As a method of reacting in the presence of a solvent, for example, suspending a solid polyalkylaluminoxane in a solvent, adding a halohydrin having 1 to 20 carbon atoms or a compound having 6 carbon atoms The above and 20 or less methods of halogenated phenols, etc.

The solvent may be any solvent as long as it is inactive to the solid polyalkylaluminoxane. For example, aromatic hydrocarbon solvents, such as benzene and toluene; Aliphatic hydrocarbon solvents, such as hexane and heptane, etc. are mentioned. The solvent may be used alone or in combination of two or more, and the amount used is preferably 1 part by weight or more and 200 parts by weight or less, more preferably 3 parts by weight or more and 1 part by weight of the solid polyalkylaluminoxane. 50 parts by weight or less.

As the modified solid polyalkylaluminoxane, a slurry obtained by reacting in the presence of a solvent may be used as it is, or a solid obtained by removing a supernatant liquid by filtration or the like, washing with a solvent, and drying may be used.

The temperature at which solid polyalkylaluminoxane reacts with halogenated alcohols or halogenated phenols is preferably -100°C or higher and not higher than the boiling point of the solvent, more preferably -80°C or higher and 100°C or lower.

Modified solid polyalkylaluminoxanes can be used in olefin oligomerization reactions. The olefin oligomerization reaction refers to a reaction in which an olefin having a carbon number that is a multiple of the number of carbon atoms of the olefin is obtained from an olefin. For example, the reaction of producing 1-butene, 1-hexene, 1-octene, etc. from ethylene; the reaction of producing 4-methyl-1-pentene, etc. from propylene. The olefin oligomerization reaction using a modified solid polyalkylaluminoxane is preferably a reaction for producing α-olefin from ethylene, more preferably a reaction for producing 1-hexene or 1-octene from ethylene.

The catalyst for olefin oligomerization reaction contains a modified solid polyalkylaluminoxane and a transition metal complex.

Examples of transition metal complexes include transition metal complexes represented by the following general formula (2-1), transition metal complexes represented by the following general formula (2-2), and transition metal complexes represented by the following general formula A transition metal complex represented by (2-3), a transition metal complex represented by the following general formula (2-4), or a transition metal complex represented by the following general formula (2-5) .

Carry out for the transition metal complex shown in general formula (2-1), the transition metal complex shown in general formula (2-2) and the transition metal complex shown in general formula (2-3) Detailed description.

[M in general formula ( ^2-1 ), general formula (2-2) and general formula (2-3) is the transition metal atom of the 4th group of the periodic table of elements;

X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , in general formula (2-1), general formula (2-2), and general formula (2-3), R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in general formula (2-2) and general formula (2-3), and general formula (2 R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ in -3) are each independently

Hydrogen atom, halogen atom, hydrocarbon group with 1 to 20 carbon atoms, substituted hydrocarbon group with 1 to 20 carbon atoms, hydrocarbon oxy group with 1 to 20 carbon atoms, 1 to 20 substituted hydrocarbyloxy groups, substituted silyl groups, or disubstituted amino groups;

Two selected from R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups with 1 to 20 carbon atoms, substituted hydrocarbon groups with 1 to 20 carbon atoms, and 1 or more carbon atoms and 20 or less hydrocarbyloxy groups, or substituted hydrocarbyloxy groups with 1 to 20 carbon atoms, the aforementioned two selected from R ¹ , R ² , R ³ and R ⁴ are optionally substituted from each Bonding at the site where the hydrogen atom has been removed from the base;

Two selected from R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a carbon number When it is a hydrocarbyloxy group of 1 to 20 or less, or a substituted hydrocarbyloxy group with 1 to 20 carbon atoms, the aforementioned two selected from R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ optionally bonded at the site where a hydrogen atom has been removed from each substituent;

In addition, two selected from R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrocarbon groups with 1 to 20 carbon atoms, substituted hydrocarbon groups with 1 to 20 carbon atoms, carbon In the case of a hydrocarbyloxy group having 1 to 20 atoms, or a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, the aforementioned selected from R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Both are optionally bonded at a site where a hydrogen atom has been removed from each substituent;

Two selected from R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a carbon number When it is a hydrocarbyloxy group with 1 to 20 carbon atoms, or a substituted hydrocarbyloxy group with 1 to 20 carbon atoms, the above is selected from two of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ optionally bonded at the site where a hydrogen atom has been removed from each substituent;

R ¹⁰ in the general formula (2-1), and R ¹¹ in the general formula (2-1) and the general formula (2-2) are each independently a hydrocarbon group having 1 to 20 carbon atoms, a carbon atom A substituted hydrocarbyl group having a number of 1 to 20, a hydrocarbyloxy group having a carbon number of 1 to 20, a substituted hydrocarbyloxy group having a carbon number of 1 to 20, a substituted silyl group, or a bis Substituted amino group;

R ¹⁰ and R ¹¹ are optionally bonded at the site where a hydrogen atom is removed from each substituent].

Examples of elements of Group ⁴ of the periodic table in M1 include titanium atoms, zirconium atoms, and hafnium atoms, among which titanium atoms are preferred.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R Examples of the halogen atom in ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ include fluorine atom, chlorine atom, bromine atom, iodine atom, and the like.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ are hydrocarbon groups having 1 to 20 carbon atoms, examples of which include 1 to 20 carbon atoms An alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the like.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl , cyclobutyl, n-pentyl, isopentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1, 2-Dimethylpropyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl group, n-hexadecyl, n-octadecyl, n-eicosyl, 1-adamantyl, etc. The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, or neopentyl.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, and 2,3-dimethylphenyl , 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl , 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3 ,4,5-Trimethylphenyl, 2,3,4,5-Tetramethylphenyl, 2,3,4,6-Tetramethylphenyl, 2,3,5,6-Tetramethylphenyl Phenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, isobutylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, anthracenyl Wait. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, more preferably phenyl, methylphenyl, dimethylphenyl, or trimethyl phenyl.

Examples of the aralkyl group having 7 to 20 carbon atoms include 1-methyl-1-phenylethyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl) phenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5- Dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl , (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, ( 3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, ( 2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl ) methyl, (n-propylphenyl) methyl, (isopropylphenyl) methyl, (n-butylphenyl) methyl, (sec-butylphenyl) methyl, (tert-butylphenyl ) methyl, (isobutylphenyl) methyl, (n-pentylphenyl) methyl, (neopentylphenyl) methyl, (n-hexylphenyl) methyl, (n-octylphenyl) Methyl, (n-decylphenyl)methyl, (n-dodecylphenyl)methyl, naphthylmethyl, anthracenylmethyl, etc. The aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms, more preferably a benzyl group.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ are substituted hydrocarbon groups having 1 to 20 carbon atoms, preferably at least one hydrogen atom present in the hydrocarbon group is replaced by A group obtained by substituting a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Examples of the substituted hydrocarbon group having 1 to 20 carbon atoms include a substituted alkyl group having 1 to 20 carbon atoms, a substituted aryl group having 6 to 20 carbon atoms, a carbon A substituted aralkyl group whose number is 7 or more and 20 or less, or the like.

The substituted alkyl group having 1 to 20 carbon atoms is preferably a substituted alkyl group having 1 to 10 carbon atoms, for example, fluoromethyl, difluoromethyl, trifluoromethyl , chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluoro Hexyl etc.

The substituted aryl group having 6 to 20 carbon atoms is preferably a substituted aryl group having 6 to 10 carbon atoms, for example, fluorophenyl, difluorophenyl, trifluorophenyl , tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl, iodophenyl, etc.

The substituted aralkyl group having 7 to 20 carbon atoms is preferably a substituted aralkyl group having 7 to 10 carbon atoms, for example, (fluorophenyl)methyl, (difluoro Phenyl) methyl, (trifluorophenyl) methyl, (tetrafluorophenyl) methyl, (pentafluorophenyl) methyl, (chlorophenyl) methyl, (bromophenyl) methyl, ( Iodophenyl) methyl, etc.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ^14. Hydrocarbyloxy groups having 1 to 20 carbon atoms in R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ include 1 to 20 carbon atoms. The following alkoxy groups, aryloxy groups having 6 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, and the like.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy , isobutoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n- Tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-di Decyloxy etc. The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably methoxy, ethoxy, isopropoxy, or tert-butyl Oxygen.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3- Dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy , 3,5-Dimethylphenoxy, 2,3,4-Trimethylphenoxy, 2,3,5-Trimethylphenoxy, 2,3,6-Trimethylphenoxy , 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethyl phenylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propyl phenylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, isobutylphenoxy, n-hexylphenoxy, n-octylbenzene Oxygen, n-decylphenoxy, n-tetradecylphenoxy, naphthyloxy and anthracenyloxy, etc. The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 10 carbon atoms, more preferably phenoxy, 2-methylphenoxy, and 3-methyl Phenoxy, or 4-methylphenoxy.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, ( 4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl) base)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy , (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy base, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy Oxygen, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6- Tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (n-propylphenyl)methoxy, (isopropylphenyl)methoxy Oxygen, (n-butylphenyl)methoxy, (sec-butylphenyl)methoxy, (tert-butylphenyl)methoxy, (isobutylphenyl)methoxy, (n-hexyl Phenyl)methoxy, (n-octylphenyl)methoxy, (n-decylphenyl)methoxy, naphthalenemethoxy, anthracenemethoxy and the like. The aralkyloxy group having 7 to 20 carbon atoms is preferably an aralkyloxy group having 7 to 10 carbon atoms, more preferably a benzyloxy group.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ are substituted hydrocarbyloxy groups having 1 to 20 carbon atoms, preferably at least A substituent in which one hydrogen atom is replaced by a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Examples of the substituted hydrocarbyloxy group having 1 to 20 carbon atoms include substituted alkoxy groups having 1 to 20 carbon atoms and substituted aryloxy groups having 6 to 20 carbon atoms. group, a substituted aralkyloxy group having 7 to 20 carbon atoms, and the like.

The substituted alkoxy group having 1 to 20 carbon atoms is preferably a substituted alkoxy group having 1 to 10 carbon atoms, for example, fluoromethoxy, difluoromethoxy, Trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, bromomethoxy, dibromomethoxy, tribromomethoxy, fluoroethoxy, perfluoropropoxy , perfluorobutoxy, perfluoropentyloxy, perfluorohexyloxy, etc.

The substituted aryloxy group having 6 to 20 carbon atoms is preferably a substituted aryloxy group having 6 to 10 carbon atoms, for example, fluorophenoxy, difluorophenoxy, Trifluorophenoxy, tetrafluorophenoxy, pentafluorophenoxy, chlorophenoxy, bromophenoxy, iodophenoxy, etc.

The substituted aralkyloxy group having 7 to 20 carbon atoms is preferably a substituted aralkyloxy group having 7 to 10 carbon atoms, for example, (fluorophenyl)methoxy Base, (difluorophenyl) methoxy, (trifluorophenyl) methoxy, (tetrafluorophenyl) methoxy, (pentafluorophenyl) methoxy, (chlorophenyl) methoxy , (bromophenyl) methoxy, (iodophenyl) methoxy, etc.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R The substituted silyl groups in ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ include, for example, substituents represented by the following general formula (I).

General formula (I): -Si(R ²² ) ₃

(3 R ²² each independently represent a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms in the 3 R ²² is 1 or more and 20 or less).

As the hydrocarbon group in ^R22 , methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, Alkyl groups having 1 to 10 carbon atoms such as n-heptyl, n-octyl, n-nonyl and n-decyl; aryl groups such as phenyl; and the like.

The halogenated hydrocarbon group in ^R22 is a group obtained by replacing at least one hydrogen atom present on the aforementioned hydrocarbon group with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The total number of carbon atoms of the three ^R22s is from 1 to 20, preferably from 3 to 18.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ substituted silyl groups include, for example, methylsilyl, ethylsilyl, phenylsilyl Silyl groups, monosubstituted silyl groups such as groups obtained by replacing at least one hydrogen atom present on these substituents with halogen atoms; dimethylsilyl, diethylsilyl, diphenylsilyl Disubstituted silyl groups such as groups obtained by replacing at least one hydrogen atom present on these substituents with halogen atoms; trimethylsilyl, triethylsilyl, tri-n-propylsilyl, Triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, triisobutylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, a group obtained by replacing at least one hydrogen atom present on these substituents with a halogen atom and other trisubstituted silyl groups and the like. The substituted silyl group is preferably a trisubstituted silyl group, more preferably trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl , a triphenylsilyl group, a tert-butyldiphenylsilyl group, or a group in which at least one hydrogen atom present in these substituents is replaced by a halogen atom.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R Examples of disubstituted amino groups in ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ include substituents represented by the following general formula (II).

General formula (II): -N(R ²³ ) ₂

(The two ^R23s each independently represent a hydrocarbon group or a halogenated hydrocarbon group, and the total number of carbon atoms of the two R23s is 2 or more and ²⁰ or less).

As the hydrocarbon group or halogenated hydrocarbon group in ^R23 , the same groups as those mentioned above for the hydrocarbon group and halogenated hydrocarbon group in ^R22 can be mentioned. The total number of carbon atoms of the two R23s is 2 to ²⁰ , preferably 2 to 10. In addition, two R ²³ are optionally bonded at the site where a hydrogen atom is removed from each substituent.

As X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , the disubstituted amino group in R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ includes, for example, dimethylamino, diethylamino, di-n-propylamino, Diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, diisobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decyl ylamino group, diphenylamino group, pyrrolidinyl group, piperidinyl group, indolinyl group, dihydroisoindolyl group, a group in which at least one hydrogen atom present in these groups is replaced by a halogen atom, and the like. The disubstituted amino group is preferably a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a piperidinyl group, or a group in which at least one hydrogen atom present in these groups is replaced by a halogen atom.

Two selected from R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups with 1 to 20 carbon atoms, substituted hydrocarbon groups with 1 to 20 carbon atoms, and 1 or more carbon atoms and 20 or less hydrocarbyloxy groups, or substituted hydrocarbyloxy groups with 1 to 20 carbon atoms, the aforementioned two selected from R ¹ , R ² , R ³ and R ⁴ are optionally substituted from each Bonding at the site where the hydrogen atom has been removed from the base;

Two selected from R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a carbon number When it is a hydrocarbyloxy group of 1 to 20 or less, or a substituted hydrocarbyloxy group with 1 to 20 carbon atoms, the aforementioned two selected from R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ Bonding is optionally performed at a site where a hydrogen atom is removed from each substituent.

In addition, two selected from R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrocarbon groups with 1 to 20 carbon atoms, substituted hydrocarbon groups with 1 to 20 carbon atoms, carbon In the case of a hydrocarbyloxy group having 1 to 20 atoms, or a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, the aforementioned selected from R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Both are optionally bonded at a site where a hydrogen atom has been removed from each substituent;

Two selected from R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a carbon number When it is a hydrocarbyloxy group with 1 to 20 carbon atoms, or a substituted hydrocarbyloxy group with 1 to 20 carbon atoms, the above is selected from two of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ Bonding is optionally performed at a site where a hydrogen atom is removed from each substituent. Examples of the ring formed by bonding at the site where the hydrogen atom is removed from each substituent include saturated or unsaturated hydrocarbyl rings, saturated or unsaturated silahydrocarbyl rings, and the like, for example, cyclopropane ring, cyclopropene ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cycloheptene ring, cyclooctane ring , cyclooctene ring, benzene ring, naphthalene ring, anthracene ring, silacyclopropane ring, silacyclobutane ring, silacyclopentane ring, silacyclohexane ring, etc. This ring is optionally substituted with a hydrocarbon group having 1 to 20 carbon atoms.

R ¹ , R ² , R ³ and R ⁴ are each independently preferably a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, a halogen atom, or a carbon group of An alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, or an aralkyl group of 7 to 20 carbon atoms, more preferably an alkyl group of 1 to 20 carbon atoms Alkyl, most preferably methyl.

The partial structure represented by the following general formula (2) having R ¹ , R ² , R ³ and R ⁴ is preferably as follows.

(R ¹ , R ² , R ³ and R ⁴ in general formula (2) and R ¹ , R in general formula (2-1), general formula (2-2), and general formula (2-3) ² , R ³ , and R ⁴ are the same).

Examples of partial structures represented by the general formula (2) include cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropyl cyclopentadienyl, and Pentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butylcyclopentadienyl, isobutylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl , tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 3-methyl Basetetrahydroindenyl, 2,3-dimethyltetrahydroindenyl, octahydrofluorenyl, etc.

As the partial structure represented by the above general formula (2), trimethylcyclopentadienyl, tetramethylcyclopentadienyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 3- Methyltetrahydroindenyl, 2,3-dimethyltetrahydroindenyl, or octahydrofluorenyl.

As R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ , preferably each independently is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.

R ⁶ , R ⁸ , R ¹³ , R ¹⁵ , R ¹⁸ and R ²⁰ are more preferably a substituted hydrocarbon group having 1 to 20 carbon atoms, and still more preferably a substituted alkyl group having 1 to 20 carbon atoms. base.

^The partial structure represented by the following general formula ( ³ ) having R ⁵ , ^{R 6} , ^{R 7} , ^{R 8} and R ⁹ , the following general formula ( The partial structure represented by 4) and the partial structure represented by the following general formula (5) having R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently preferably as follows.

(R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in general formula (3) and R in general formula (2-1), general formula (2-2), and general formula (2-3) ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same).

(R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in general formula (4) and R ¹² , R ¹³ , R ¹⁴ , R in general formula (2-2) and general formula (2-3) ¹⁵ and R ¹⁶ are the same).

(R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ in general formula (5) are the same as R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ in general formula (2-3)).

As the partial structure represented by the above general formula (3), the partial structure represented by the general formula (4) and the partial structure represented by the general formula (5), phenyl, methylphenyl, dimethylbenzene Base, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, diisopropylphenyl, tert-butylphenyl, Di-tert-butylphenyl, tert-butylmethylphenyl, di-tert-butylmethylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl, bis(trifluoromethyl ) phenyl, biphenyl, benzyl phenyl, methoxyphenyl, phenoxyphenyl, benzyloxyphenyl, (trimethylsilyl) phenyl, (dimethylamino ) phenyl, etc.

As the partial structure represented by the above general formula (3), the partial structure represented by the general formula (4) and the partial structure represented by the general formula (5), more preferably phenyl, methylphenyl, dimethylbenzene group, trimethylphenyl, diethylphenyl, or (trimethylsilyl)phenyl. In addition, the partial structure represented by the general formula (3), the partial structure represented by the general formula (4), and the partial structure represented by the general formula (5) may be the same or different.

R ¹⁰ and R ¹¹ are each independently preferably a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, Or an aralkyl group having 7 or more and 20 or less carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, or benzene methyl.

In the general formula (2-1), the partial structure represented by the following general formula (6) having R ¹⁰ and R ¹¹ is preferably as follows.

(R ¹⁰ and R ¹¹ in the general formula (6) are the same as R ¹⁰ and R ¹¹ in the general formula (2-1)).

Dimethylsilanediyl, diethylsilanediyl, ethylmethylsilanediyl, di-n-propylsilanediyl, methyl-n-propylsilanediyl, di-n-butylsilanediyl, n-butylmethylsilane Diylsilanediyl, n-hexylmethylsilanediyl, methyl-n-octylsilanediyl, n-decylmethylsilanediyl, methyl-n-octadecylsilanediyl, cyclohexylmethylsilanediyl group, silacyclopentane-1,1-diyl, silacyclohexane-1,1-diyl.

As the partial structure represented by the above-mentioned general formula (6), it is more preferable that R ¹⁰ is the same structure as R ¹¹ , and it is more preferable that it is dimethylsilanediyl, diethylsilanediyl, or silacyclopentane-1 ,1-diyl, silacyclohexane-1,1-diyl.

X ¹ , X ² and X ³ in general formula (2-1), general formula (2-2), and general formula (2-3) are preferably each independently a halogen atom, and the number of carbon atoms is 1 to 20 The following hydrocarbon groups, substituted hydrocarbon groups having 1 to 20 carbon atoms, more preferably alkyl groups having 1 to 20 carbon atoms, substituted alkyl groups having 1 to 20 carbon atoms, carbon An aralkyl group having 7 to 20 atoms, or a substituted aralkyl group having 7 to 20 carbon atoms, more preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, or A substituted alkyl group having 1 to 20 carbon atoms.

Examples of the transition metal complex represented by the general formula (2-1) include titanium chloride complexes described below.

(1-(Dimethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diethylphenylsilyl)- 2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(phenyldi-n-propylsilyl)-2,3,4,5-tetramethylcyclopentadiene Dienyl)titanium trichloride, (1-(diisopropylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-( Di-n-butylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diisobutylphenylsilyl)-2, 3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(di-sec-butylphenylsilyl)-2,3,4,5-tetramethylcyclopentadiene base) titanium trichloride, 1-(di-tert-butylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl) titanium trichloride, (1-(ethyl methyl (phenylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methylphenyl-n-propylsilyl)-2,3 ,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methylphenylisopropylsilyl)-2,3,4,5-tetramethylcyclopentadiene base) titanium trichloride, (1-(n-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl) titanium trichloride, (1-(isobutylmethyl Phenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(sec-butylmethylphenylsilyl)-2,3,4,5 -tetramethylcyclopentadienyl)titanium, (1-(tert-butylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1 -(cyclohexylmethylphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl-n-octadecylphenylmethyl silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride,

(1-(Dimethyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(di Ethyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-((3,5-di Methylphenyl)di-n-propylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diisopropyl(3,5-di Methylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium, (1-(di-n-butyl(3,5-dimethylphenyl)silane base)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diisobutyl(3,5-dimethylphenyl)silyl)-2 ,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(di-sec-butyl(3,5-dimethylphenyl)silyl)-2,3,4 ,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(di-tert-butyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetra Methylcyclopentadienyl)titanium trichloride, (1-(ethylmethyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadiene Dienyl)titanium trichloride, (1-(methyl(3,5-dimethylphenyl)-n-propylsilyl)-2,3,4,5-tetramethylcyclopentadiene base) titanium trichloride, (1-(methyl(3,5-dimethylphenyl) isopropylsilyl)-2,3,4,5-tetramethylcyclopentadienyl) tri Titanium chloride, (1-(n-butylmethyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, ( 1-(isobutylmethyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(sec-butylmethyl) (3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(tert-butylmethyl(3,5 -Dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(cyclohexylmethyl(3,5-dimethyl Phenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl-n-octadecyl(3,5-dimethyl phenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride.

In addition, it is also possible to replace "2,3,4,5-tetramethylcyclopentadienyl" in the above-mentioned titanium chloride complex with "cyclopentadienyl", "2-methylcyclopentadienyl" in the same manner. Cyclopentadienyl", "3-methylcyclopentadienyl", "2,3-dimethylcyclopentadienyl", "2,4-dimethylcyclopentadienyl", "2,5-Dimethylcyclopentadienyl", "2,3,5-trimethylcyclopentadienyl", "2-ethylcyclopentadienyl", "3-ethylcyclopentadienyl" Pentadienyl", "2-n-propylcyclopentadienyl", "3-n-propylcyclopentadienyl", "2-isopropylcyclopentadienyl", "3-isopropyl Cyclopentadienyl", "2-n-butylcyclopentadienyl", "3-n-butylcyclopentadienyl", "2-sec-butylcyclopentadienyl", "3-sec-butylcyclopentadienyl ", "2-tert-butylcyclopentadienyl", "3-tert-butylcyclopentadienyl", "2-phenylcyclopentadienyl", "3-phenylcyclopentadienyl", "2 -benzylcyclopentadienyl", "3-benzylcyclopentadienyl", "indenyl", "2-methylindenyl", "fluorenyl", "tetrahydroindenyl", Titanium chloride complexes obtained from "2-methyltetrahydroindenyl" or "octahydrofluorenyl".

Further, zirconium chloride complexes obtained by replacing "titanium" with "zirconium" in the titanium chloride complexes exemplified above, hafnium chloride obtained by replacing "hafnium" can also be exemplified in the same manner. Chlorinated transition metal complexes such as complexes; titanium fluoride complexes obtained by replacing "chlorine" with "fluorine" in the titanium chloride complexes exemplified above, and those obtained by replacing "bromine" Titanium bromide complexes, titanium iodide complexes obtained by substituting "iodine" and other titanium halide complexes; obtained by substituting "chlorine" for "hydrogen" in the titanium chloride complexes exemplified above Titanium hydride complexes, alkyl titanium complexes such as methyl titanium complexes obtained by replacing "methyl"; replace "chlorine" in the titanium chloride complexes exemplified above with "phenyl Aryltitanium complexes such as phenyltitanium complexes obtained; benzyltitanium complexes obtained by replacing "chlorine" in the titanium chloride complexes exemplified above with "benzyl" and other aralkyltitanium complexes; methoxytitanium complexes obtained by replacing "chlorine" in the titanium chloride complexes exemplified above with "methoxo", and " Alkanes such as n-butoxy titanium complexes obtained by n-butoxylation (n-butoxo), and isopropoxy titanium complexes obtained by replacing them with "isopropoxylation (isopropoxo)" Alkoxo-titanium complexes (alkoxo-titanium complexes); phenoxy-titanium complexes obtained by replacing "chlorine" in the titanium chloride complexes exemplified above with "phenoxo" aryloxo-titanium complexes; benzyloxy obtained by replacing "chlorine" in the titanium chloride complexes exemplified above with "benzyloxo" Aralkyloxo-titanium complexes such as aralkyloxo-titanium complexes; replace "chlorine" in the titanium chloride complexes exemplified above with "dimethylamido" Amido-titanium complexes such as the obtained dimethylamide titanium complex and the diethylamide titanium complex obtained by replacing it with "diethylamido".

Examples of the transition metal complex represented by the general formula (2-2) include titanium chloride complexes described below.

(1-(methyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(ethyldiphenylsilyl)- 2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(n-propyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadiene Dienyl)titanium trichloride, (1-(isopropyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-( n-Butyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(isobutyldiphenylsilyl)-2, 3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-sec-butyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl ) titanium trichloride, (1-(tert-butyldiphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl) titanium trichloride, (1-(cyclohexyl di Phenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(n-octadecyldiphenylsilyl)-2,3, 4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methylphenyl(2-methylphenyl)silyl)-2,3,4,5-tetramethyl Cyclopentadienyl)titanium trichloride, (1-(methylphenyl(3-methylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)tri Titanium chloride, (1-(methylphenyl(4-methylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1- (Methylphenyl(2,3-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methylbenzene (2,4-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methylphenyl(2, 5-Dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methylphenyl(2,6-dimethyl phenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methylphenyl(3,5-dimethylphenyl) Silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methylphenyl(3,4,5-trimethylphenyl)silane base)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride,

(1-(Ethylphenyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-( n-Propylphenyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(isopropyl Phenyl(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(n-butylphenyl( 3,5-Dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(isobutylphenyl(3,5 -Dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(sec-butylphenyl(3,5-dimethyl phenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(tert-butylphenyl(3,5-dimethylphenyl )silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(cyclohexylphenyl(3,5-dimethylphenyl)silyl )-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(n-octadecylphenyl(3,5-dimethylphenyl)silyl) -2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl(2-methylphenyl)(3,5-dimethylphenyl)silane base)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl(3-methylphenyl)(3,5-dimethylphenyl) Silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl(4-methylphenyl)(3,5-dimethylbenzene base)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl(2,3-dimethylphenyl)(3,5 -Dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl(2,4-dimethylphenyl )(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl(2,5- Dimethylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl (2,6-dimethylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, ( 1-(Methylbis(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(methyl (3,5-Dimethylphenyl)(3,4,5-trimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride .

In addition, it is also possible to replace "2,3,4,5-tetramethylcyclopentadienyl" in the above-mentioned titanium chloride complex with "cyclopentadienyl", "2-methylcyclopentadienyl" in the same manner. Cyclopentadienyl", "3-methylcyclopentadienyl", "2,3-dimethylcyclopentadienyl", "2,4-dimethylcyclopentadienyl", "2,5-Dimethylcyclopentadienyl", "2,3,5-trimethylcyclopentadienyl", "2-ethylcyclopentadienyl", "3-ethylcyclopentadienyl" Pentadienyl", "2-n-propylcyclopentadienyl", "3-n-propylcyclopentadienyl", "2-isopropylcyclopentadienyl", "3-isopropyl Cyclopentadienyl", "2-n-butylcyclopentadienyl", "3-n-butylcyclopentadienyl", "2-sec-butylcyclopentadienyl", "3-sec-butylcyclopentadienyl ", "2-tert-butylcyclopentadienyl", "3-tert-butylcyclopentadienyl", "2-phenylcyclopentadienyl", "3-phenylcyclopentadienyl", "2 -benzylcyclopentadienyl", "3-benzylcyclopentadienyl", "indenyl", "2-methylindenyl", "fluorenyl", "tetrahydroindenyl", Titanium chloride complexes obtained from "2-methyltetrahydroindenyl" or "octahydrofluorenyl".

Further, zirconium chloride complexes obtained by replacing "titanium" with "zirconium" in the titanium chloride complexes exemplified above, hafnium chloride obtained by replacing "hafnium" can also be exemplified in the same manner. Chlorinated transition metal complexes such as complexes; titanium fluoride complexes obtained by replacing "chlorine" with "fluorine" in the titanium chloride complexes exemplified above, and those obtained by replacing "bromine" Titanium bromide complexes, titanium iodide complexes obtained by substituting "iodine" and other titanium halide complexes; obtained by substituting "chlorine" for "hydrogen" in the titanium chloride complexes exemplified above Titanium hydride complexes, alkyl titanium complexes such as methyl titanium complexes obtained by replacing "methyl"; replace "chlorine" in the titanium chloride complexes exemplified above with "phenyl Aryltitanium complexes such as phenyltitanium complexes obtained; benzyltitanium complexes obtained by replacing "chlorine" in the titanium chloride complexes exemplified above with "benzyl" Aralkyltitanium complexes such as aralkyltitanium complexes; methoxytitanium complexes obtained by replacing "chlorine" in the titanium chloride complexes exemplified above with "methoxylate", and "n-butoxy Alkoxylated titanium complexes such as n-butoxylated titanium complexes obtained by substituting "isopropoxylated titanium complexes" for "isopropoxylated" titanium complexes; Aryloxylated titanium complexes such as phenoxylated titanium complexes obtained by replacing "chlorine" in the titanium chloride complex with "phenoxylated"; aralkyloxy titanium complexes such as benzyloxy titanium complexes obtained by replacing "chlorine" in the compound with "benzyl oxylate"; Titanium amides such as dimethylamide titanium complexes obtained by replacing "chlorine" with "dimethylamination" and diethylamide titanium complexes obtained by replacing "diethylamination" complexes.

Examples of the transition metal complex represented by the general formula (2-3) include titanium chloride complexes described below.

(1-(triphenylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(phenylbis(2-methylphenyl)methyl Silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(phenylbis(3-methylphenyl)silyl)-2,3, 4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(phenylbis(4-methylphenyl)silyl)-2,3,4,5-tetramethylcyclo Pentadienyl)titanium trichloride, (1-(phenylbis(2,3-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl) Titanium trichloride, (1-(phenylbis(2,4-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl) titanium trichloride, (1-(phenylbis(2,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(benzene Bis(2,6-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(phenylbis(3, 5-Dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(phenylbis(3,4,5-tri Methylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride,

(1-(diphenyl(2-methylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diphenyl( 3-methylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diphenyl(4-methylphenyl)methyl Silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diphenyl(2,3-dimethylphenyl)silyl)-2 ,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diphenyl(2,4-dimethylphenyl)silyl)-2,3,4, 5-tetramethylcyclopentadienyl)titanium trichloride, (1-(diphenyl(2,5-dimethylphenyl)silyl)-2,3,4,5-tetramethyl Cyclopentadienyl)titanium trichloride, (1-(diphenyl(2,6-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl ) titanium trichloride, (1-(diphenyl(3,5-dimethylphenyl) silyl)-2,3,4,5-tetramethylcyclopentadienyl) titanium trichloride , (1-diphenyl(3,4,5-trimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride,

(1-(phenyl(2-methylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl) trichloride Titanium, (1-(phenyl(3-methylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)tri Titanium chloride, (1-(phenyl(4-methylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl ) titanium trichloride, (1-(phenyl(2,3-dimethylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethyl Cyclopentadienyl)titanium trichloride, (1-(phenyl(2,4-dimethylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4, 5-tetramethylcyclopentadienyl)titanium trichloride, (1-(phenyl(2,5-dimethylphenyl)(3,5-dimethylphenyl)silyl)-2 ,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-phenyl(2,6-dimethylphenyl)(3,5-dimethylphenyl)silane base)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(phenyl(3,5-dimethylphenyl)(3,4,5-tri Methylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride,

(1-(bis(2-methylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride , (1-(bis(3-methylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl) trichloride Titanium, (1-(bis(4-methylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadienyl)trichloro Titanium oxide, (1-(bis(2,3-dimethylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethylcyclopentadiene base) titanium trichloride, (1-(bis(2,4-dimethylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethyl Cyclopentadienyl)titanium trichloride, (1-(bis(2,5-dimethylphenyl)(3,5-dimethylphenyl)silyl)-2,3,4,5 -Tetramethylcyclopentadienyl)titanium trichloride, (1-(bis(2,6-dimethylphenyl)(3,5-dimethylphenyl)silyl)-2,3 ,4,5-tetramethylcyclopentadienyl)titanium trichloride, (1-(tris(3,5-dimethylphenyl)silyl)-2,3,4,5-tetramethyl Cyclopentadienyl)titanium trichloride, (1-((3,5-dimethylphenyl)bis(3,4,5-dimethylphenyl)silyl)-2,3, 4,5-Tetramethylcyclopentadienyl) titanium trichloride.

In addition, it is also possible to replace "2,3,4,5-tetramethylcyclopentadienyl" in the above-mentioned titanium chloride complex with "cyclopentadienyl", "2-methylcyclopentadienyl" in the same manner. Cyclopentadienyl", "3-methylcyclopentadienyl", "2,3-dimethylcyclopentadienyl", "2,4-dimethylcyclopentadienyl", "2,5-Dimethylcyclopentadienyl", "2,3,5-trimethylcyclopentadienyl", "2-ethylcyclopentadienyl", "3-ethylcyclopentadienyl" Pentadienyl", "2-n-propylcyclopentadienyl", "3-n-propylcyclopentadienyl", "2-isopropylcyclopentadienyl", "3-isopropyl Cyclopentadienyl", "2-n-butylcyclopentadienyl", "3-n-butylcyclopentadienyl", "2-sec-butylcyclopentadienyl", "3-sec-butylcyclopentadienyl ", "2-tert-butylcyclopentadienyl", "3-tert-butylcyclopentadienyl", "2-phenylcyclopentadienyl", "3-phenylcyclopentadienyl", "2 -benzylcyclopentadienyl", "3-benzylcyclopentadienyl", "indenyl", "2-methylindenyl", "fluorenyl", "tetrahydroindenyl", Titanium chloride complexes obtained from "2-methyltetrahydroindenyl" or "octahydrofluorenyl".

Further, zirconium chloride complexes obtained by replacing "titanium" with "zirconium" in the titanium chloride complexes exemplified above, hafnium chloride obtained by replacing "hafnium" can also be exemplified in the same manner. Chlorinated transition metal complexes such as complexes; titanium fluoride complexes obtained by replacing "chlorine" with "fluorine" in the titanium chloride complexes exemplified above, and those obtained by replacing "bromine" Titanium bromide complexes, titanium iodide complexes obtained by substituting "iodine" and other titanium halide complexes; obtained by substituting "chlorine" for "hydrogen" in the titanium chloride complexes exemplified above Titanium hydride complexes, alkyl titanium complexes such as methyl titanium complexes obtained by replacing "methyl"; replace "chlorine" in the titanium chloride complexes exemplified above with "phenyl Aryltitanium complexes such as phenyltitanium complexes obtained; benzyltitanium complexes obtained by replacing "chlorine" in the titanium chloride complexes exemplified above with "benzyl" Aralkyltitanium complexes such as aralkyltitanium complexes; methoxytitanium complexes obtained by replacing "chlorine" in the titanium chloride complexes exemplified above with "methoxylate", and "n-butoxy Alkoxylated titanium complexes such as n-butoxylated titanium complexes obtained by substituting "isopropoxylated titanium complexes" for "isopropoxylated" titanium complexes; Aryloxylated titanium complexes such as phenoxylated titanium complexes obtained by replacing "chlorine" in the titanium chloride complex with "phenoxylated"; aralkyloxy titanium complexes such as benzyloxy titanium complexes obtained by replacing "chlorine" in the compound with "benzyl oxylate"; Titanium amides such as dimethylamide titanium complexes obtained by replacing "chlorine" with "dimethylamination" and diethylamide titanium complexes obtained by replacing "diethylamination" complexes.

Examples of methods for producing transition metal complexes represented by general formula (2-1), (2-2), or (2-3) include JP-A-2011-98954 and JP-A-2013-184926 method described in No.

The transition metal complex represented by the general formula (2-4) and the transition metal complex represented by the general formula (2-5) will be described in detail.

[M in the general formula (2-4) ² is the transition metal atom of the 4th group of the periodic table of elements;

A ²¹ is an oxygen atom, nitrogen atom, phosphorus atom or sulfur atom, Z ¹ is a group connecting A ²¹ and N, the shortest number of bonds connecting A ²¹ and N is 4 or more and 6 or less, connecting A ²¹ and Z ¹ The bond of is optionally a double bond;

R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ , and X ⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom A substituted hydrocarbyl group of 1 to 20 carbon atoms, a hydrocarbyloxy group of 1 to 20 carbon atoms, a substituted hydrocarbyloxy group of 1 to 20 carbon atoms, a substituted silyl group, or a disubstituted amino group ;

Two selected from R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a carbon number When it is a hydrocarbyloxy group of 1 to 20 or less, or a substituted hydrocarbyloxy group with 1 to 20 carbon atoms, the aforementioned is selected from two of R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ optionally bonded at the site where a hydrogen atom has been removed from each substituent;

^R29 is a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon forkide group with 1 to 20 carbon atoms, or In a substituted alkylidene group having 1 to 20 carbon atoms, the bond connecting R ²⁹ and A ²¹ is optionally a double bond; R ²⁹ is optionally bonded to Z ¹ ].

[M in the general formula (2-5) ² is the transition metal atom of the 4th group of the periodic table of elements;

A ²² is a nitrogen atom or a phosphorus atom, Z ² is a group connecting A ²² and N, and the shortest number of bonds connecting A ²² and N is not less than 4 and not more than 6;

R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ , and X ⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom A substituted hydrocarbyl group of 1 to 20 carbon atoms, a hydrocarbyloxy group of 1 to 20 carbon atoms, a substituted hydrocarbyloxy group of 1 to 20 carbon atoms, a substituted silyl group, or a disubstituted amino group ;

Two selected from R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a carbon number When it is a hydrocarbyloxy group of 1 to 20 or less, or a substituted hydrocarbyloxy group with 1 to 20 carbon atoms, the aforementioned is selected from two of R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ optionally bonded at the site where a hydrogen atom has been removed from each substituent;

R ³⁰ and R ³¹ are a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a substituted hydrocarbon group with 1 to 20 carbon atoms, and R ³⁰ or R ³¹ is optionally bonded to Z ² combine].

Examples of M ² include titanium atoms, zirconium atoms, and hafnium atoms, among which titanium atoms are preferred.

R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ , and X ⁶ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon group having 1 or more carbon atoms and A substituted hydrocarbyl group of 20 or less, a hydrocarbyloxy group of 1 to 20 carbon atoms, a substituted hydrocarbyloxy group of 1 to 20 carbon atoms, a substituted silyl group, or a disubstituted amino group, these The respective definitions and examples of atoms or substituents are the same as in the aforementioned X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ are hydrogen atoms, halogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, and carbon A substituted hydrocarbyl group having 1 to 20 atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted hydrocarbyloxy group having 1 to 20 carbon atoms, a substituted silyl group, or The same as described for the disubstituted amino group.

The number of carbon atoms of the hydrocarbon group, substituted hydrocarbon group, hydrocarbyloxy group and substituted hydrocarbyloxy group in R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ and X ⁶ is preferably 1 or more and 10 the following.

The substituted silyl group in R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ and X ⁶ is preferably a trisubstituted silyl group, a silicon atom-bonded hydrocarbon group or a halogenated hydrocarbon group The number of carbon atoms in is preferably 1 or more and 10 or less. In addition, among the substituted silyl groups, the total number of carbon atoms of the hydrocarbon groups or halogenated hydrocarbon groups bonded to silicon atoms is preferably 3 or more and 18 or less. As the substituted silyl group in R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ and X ⁶ , more preferably trimethylsilyl, triethylsilyl, tri A phenylsilyl group, a dimethylphenylsilyl group, or a substituent obtained by replacing at least one hydrogen atom existing in these substituents with a halogen atom.

Of the disubstituted amino groups among R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ , and X ⁶ , the number of carbon atoms in the hydrocarbon group or halogenated hydrocarbon group bonded to the nitrogen atom is preferably 1 or more. and 10 or less, more preferably 1 or more and 5 or less. The total number of carbon atoms in the hydrocarbon group or halogenated hydrocarbon group bonded to the nitrogen atom is preferably 2 or more and 10 or less.

Two selected from R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a carbon number When it is a hydrocarbyloxy group of 1 to 20 or less, or a substituted hydrocarbyloxy group with 1 to 20 carbon atoms, the aforementioned is selected from two of R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ Bonding is optionally performed at a site where a hydrogen atom is removed from each substituent. Examples of the ring formed by bonding at a site where a hydrogen atom is removed from each substituent include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentane ring, and a cyclopentane ring. Saturated or unsaturated hydrocarbyl rings such as alkene ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cycloheptene ring, cyclooctane ring, cyclooctene ring, benzene ring, naphthalene ring, anthracene ring, etc. At least one hydrogen atom on the ring is optionally substituted with a hydrocarbon group having 1 to 20 carbon atoms.

R ²⁴ is more preferably phenyl, 1-methyl-1-phenylethyl, tert-butyl, or 1-adamantyl, and still more preferably 1-adamantyl.

R ²⁶ is more preferably methyl, cyclohexyl, tert-butyl, or 1-adamantyl, and still more preferably methyl.

R ²⁵ , R ²⁷ and R ²⁸ are more preferably hydrogen atoms.

X ⁴ , X ⁵ and X ⁶ are more preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms, further preferably a chlorine atom, a bromine atom, or a methyl group.

A ²¹ represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom, and A ²² represents a nitrogen atom or a phosphorus atom.

R ²⁹ represents a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon forkylide group with 1 to 20 carbon atoms, a carbon In the substituted alkylidene group having 1 to 20 atoms, the bond connecting R ²⁹ and A ²¹ is optionally a double bond. The definitions and examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the substituted hydrocarbon group having 1 to 20 carbon atoms in R ²⁹ are the same as those described above for X ¹ , X ² , X ³ , and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ is the same as that described for the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, or the substituted hydrocarbon group having 1 to 20 carbon atoms in R ²¹ .

Examples of the hydrocarbon alkylidene group having 1 to 20 carbon atoms include a methylene group, an ethylidene group, a benzylidene group, and a cyclohexylidene group. The substituted hydrocarbyl group having 1 to 20 carbon atoms is, for example, a substituent in which at least one hydrogen atom existing in the hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

In ^R29 , the number of carbon atoms of the hydrocarbon group, substituted hydrocarbon group, hydrocarbon fork group and substituted hydrocarbon fork group is preferably 1 to 10, more preferably 1 to 5.

R ²⁹ is preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, or isopropyl group, and even more preferably a methyl group.

R ³⁰ and R ³¹ represent a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a halogen atom, a carbon atom in R ³⁰ and R ³¹ The meaning and examples of the hydrocarbon group having 1 to 20 carbon atoms or the substituted hydrocarbon group having 1 to 20 carbon atoms are the same as those described above for X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and halogen atoms in R ²¹ , a hydrocarbon group having 1 to 20 carbon atoms, or a substituted hydrocarbon group having 1 to 20 carbon atoms is the same as described.

In R ³⁰ and R ³¹ , the number of carbon atoms in the hydrocarbon group and the substituted hydrocarbon group is preferably 1 to 10, more preferably 1 to 5.

R ³⁰ is preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, or isopropyl group, and even more preferably a methyl group.

R ³¹ is preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, or isopropyl group, and even more preferably a methyl group.

Z ¹ is a group connecting A ²¹ and N, the shortest number of bonds connecting A ²¹ and N is not less than 4 and not more than 6, and the bond connecting A ²¹ and Z ¹ is optionally a double bond. Z ² is a group connecting A ²² and N, and the shortest number of bonds connecting A ²² and N is 4 or more and 6 or less. The minimum number of keys is defined by the method described in International Publication No. 2009/005003.

Examples of Z ¹ and Z ² include structures represented by the following general formula (7). Among them, the carbon atom bonded to ^R32 in the following general formula (7) is bonded to the nitrogen atom in general formula (2-4) or general formula (2-5), and the carbon atom bonded to ^R35 The atoms are bonded to A ²¹ in the general formula (2-4) or A ²² in the general formula (2-5), respectively.

[R ³² , R ³³ , R ³⁴ and R ³⁵ in the general formula (7) each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituent having 1 to 20 carbon atoms Hydrocarbyl groups with 1 to 20 carbon atoms, substituted hydrocarbyloxy groups with 1 to ²⁰ carbon atoms, R32 and ^R33 are hydrocarbon groups with 1 to 20 carbon atoms , a substituted hydrocarbyl group with 1 to 20 carbon atoms, a hydrocarbyloxy group with 1 to 20 carbon atoms, or a substituted hydrocarbyloxy group with 1 to ²⁰ carbon atoms, R32 and R ³³ is optionally bonded at the site where the hydrogen atom is removed from each substituent; R ³⁴ and R ³⁵ are a hydrocarbon group with 1 to 20 carbon atoms, a substituted substituted carbon group with 1 to 20 carbon atoms In the case of a hydrocarbyl group, a hydrocarbyloxy group with a carbon number of 1 to 20, or a substituted hydrocarbyloxy group with a carbon number of 1 to 20, ^R34 and ^R35 optionally remove hydrogen from each substituent bond at the site of the atom].

^R35 is a hydrocarbon group with 1 to 20 carbon atoms, a substituted hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbon group with 1 to 20 carbon atoms, or a hydrocarbon group with 1 or more carbon atoms And 20 or less substituted hydrocarbyloxy groups, and R ²⁹ in the general formula (2-4) or R ³¹ in the general formula (2-5) is a hydrocarbon group with a carbon number of 1 or more and 20 or less, and the number of carbon atoms When it is a substituted hydrocarbon group with 1 to 20 carbon atoms, a hydrocarbyloxy group with 1 to 20 carbon atoms, or a substituted hydrocarbon group with 1 to 20 carbon atoms, R ³⁵ and R ²⁹ , or R ³⁵ and R ³¹ are optionally bonded at a site where a hydrogen atom is removed from each substituent.

R ³² , R ³³ , R ³⁴ and R ³⁵ are hydrocarbon groups having 1 to 20 carbon atoms, substituted hydrocarbon groups having 1 to 20 carbon atoms, and hydrocarbon groups having 1 to 20 carbon atoms The definition and examples of oxy group and substituted hydrocarbyloxy group having 1 to 20 carbon atoms are the same as those described above for X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , The number of carbon atoms in R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ is 1 or more And in the hydrocarbon group of 20 or less, the substituted hydrocarbon group of 1 or more and 20 or less carbon atoms, the hydrocarbon oxy group of 1 or more and 20 or less carbon atoms, the substituted hydrocarbon group of 1 or more and 20 or less carbon atoms Same as explained.

Among R ³² , R ³³ , R ³⁴ , and R ³⁵ , the number of carbon atoms in the hydrocarbon group, substituted hydrocarbon group, hydrocarbyloxy group, and substituted hydrocarbyloxy group is preferably 1 or more and 10 or less.

As a method for producing the transition metal complex represented by the general formula (2-4) or the transition metal complex represented by the general formula (2-5), the method described in International Publication No. 2009/005003 can be mentioned .

Examples of the transition metal complex represented by the general formula (2-4) or the transition metal complex represented by the general formula (2-5) include the following compounds.

.

As the transition metal complex represented by the general formula (2-4) or the transition metal complex represented by the general formula (2-5), the following general formula (2-a) or general formula A transition metal complex represented by (2-b).

[M ² , A ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ and X ⁶ in the general formula (2-a) are respectively the same as the aforementioned M ² , A ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ and X ⁶ are the same;

Two selected from R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are optionally bonded at a position where a hydrogen atom is removed from each substituent, and each of X ⁴ , X ⁵ and X ⁶ may be the same or Different, two or more of X ⁴ , X ⁵ and X ⁶ are optionally bonded to each other to form a ring;

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each represent a hydrogen atom, or a hydrocarbon group].

[M ² , A ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ , R ³¹ , X ⁴ , X ⁵ and X ⁶ in general formula (2-b) are the same as the aforementioned M ² , A ²¹ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ , R ³¹ , X ⁴ , X ⁵ and X ⁶ are the same;

Two selected from R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are optionally bonded at a position where a hydrogen atom is removed from each substituent, and each of X ⁴ , X ⁵ and X ⁶ may be the same or Different, two or more of X ⁴ , X ⁵ and X ⁶ are optionally bonded to each other to form a ring;

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each represent a hydrogen atom, or a hydrocarbon group].

Preferred atoms for M ² in the general formula (2-a) and the general formula (2-b) are the same as those for M ² in the general formula (2-4) and (2-5).

Preferred atoms or groups of R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and X ⁴ in general formula (2-a) and general formula (2-b) and general formula (2-4) and general formula Preferred atoms or groups of R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , X ⁴ , X ⁵ and X ⁶ in formula (2-5) are the same.

Preferred groups of R ²⁹ , R ³⁰ and R ³¹ in general formula (2-a) and general formula (2-b) are the same as R ²⁹ , R 30 and R 31 in general formula (2-4) and general formula (2-5). Preferred groups for R ³⁰ and R ³¹ are the same.

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ in general formula (2-a) and general formula (2-b) represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is preferably an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 5.

As a method for producing the catalyst for olefin oligomerization reaction of the present invention, there may be mentioned a method of contacting a modified solid polyalkylaluminoxane with a transition metal complex, for example, the following method: in a solvent , making the solid polyalkylaluminoxane react with a halogenated alcohol with a carbon number of 1 to 20 or a halogenated phenol with a carbon number of 6 to 20 to obtain a modified solid polyalkylene After the aluminoxane, it is further contacted with a transition metal complex. The reaction of the solid polyalkylaluminoxane with a halogenated alcohol having 1 to 20 carbon atoms or a halogenated phenol having 6 to 20 carbon atoms is preferably carried out before contact with the transition metal complex . Some or all of these operations can be performed in the reactor used for olefin oligomerization. As the catalyst for olefin oligomerization reaction, the contacted slurry may be used as it is, or a solid obtained by removing the solvent by filtration, decantation, or distillation under reduced pressure of the solvent may be used.

The modified solid polyalkylaluminoxane and the transition metal complex are preferably brought into contact in a solvent. Examples of the solvent include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane; and aromatic hydrocarbons such as benzene and toluene. The solvent may be used alone or in combination of two or more, and the amount used is preferably 1 part by weight or more and 200 parts by weight or less, more preferably 3 parts by weight, based on 1 part by weight of the modified solid polyalkylaluminoxane. More than or equal to 50 parts by weight or less.

The temperature at which the modified solid polyalkylaluminoxane contacts the transition metal complex is usually -30°C or higher and the boiling point of the solvent or lower, preferably -10°C or higher and 120°C or lower, more preferably 0°C or higher and Below 50°C.

When the contacted slurry is used as the catalyst for olefin oligomerization reaction, the molar concentration of aluminum atoms contained in the modified solid polyalkylaluminoxane in the catalyst for olefin oligomerization reaction is usually 0.01 mmol/L The molar concentration of the transition metal complex contained in the catalyst for olefin oligomerization reaction is generally 0.0001 mmol/L to 5 mmol/L, preferably 0.02 mmol/L to 100 mmol/L , preferably 0.0002 mmol/L or more and 1 mmol/L or less.

The molar ratio of the aluminum atoms contained in the modified solid polyalkylaluminoxane to the transition metal complex is usually 1 to 10000, preferably 10 to 1000, more preferably 50 to 500.

The above catalyst for olefin oligomerization reaction may be used in combination with one or more aluminum compounds (A) represented by the general formula (A).

General formula (A) (E ¹ ) _a Al(G) _3-a

(In the general formula (A), E1 is a hydrocarbon group with a carbon number of ¹ or more and 8 or less, G is a hydrogen atom or a halogen atom, and a is a number of 1 or more and 3 or less; when a is 2 or more, a plurality of E ¹ can be the same or different from each other).

Examples of hydrocarbon groups having ¹ to 8 carbon atoms in E1 include alkyl groups having 1 to 8 carbon atoms, specifically methyl, ethyl, n-propyl, etc. Base, isopropyl, n-butyl, isobutyl, n-pentyl, neopentyl, etc.

Examples of the organoaluminum compound (A) include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride, and examples of the trialkylaluminum include trimethylaluminum aluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, etc., as dialkylaluminum chloride, for example, dimethylaluminum chloride, diethylaluminum aluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, dioctylaluminum chloride, etc. Examples of alkylaluminum dichloride include methyl dichloride Aluminum chloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, octylaluminum dichloride, etc., as dialkylaluminum hydride, for example, Dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, dioctylaluminum hydride, and the like. Trimethylaluminum, triisobutylaluminum, or trioctylaluminum are preferred.

The molar ratio of the aluminum compound (A) to the transition metal complex is usually from 1 to 100,000, preferably from 100 to 50,000. The molar concentration of the organoaluminum compound (A) is usually not less than 0.01 mmol/L and not more than 500 mmol/L, preferably not less than 0.1 mmol/L and not more than 100 mmol/L.

The catalyst for olefin oligomerization reaction of this invention can be used for an olefin oligomerization reaction, for example, can oligomerize an olefin, and can produce α-olefin. Specifically, 1-butene, 1-hexene, 1-octene, and the like can be produced from ethylene.

The catalyst for olefin oligomerization reaction of the present invention is preferably used in the reaction of producing 1-hexene or 1-octene from ethylene, more preferably used in the reaction of producing 1-hexene from ethylene.

The olefin oligomerization reaction can be carried out in solvents such as aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, aromatic hydrocarbons such as benzene and toluene, or in a slurry state, or This is done using gaseous olefins.

The olefin oligomerization reaction can be performed by any method of a batch method, a semi-continuous method, or a continuous method.

When using an olefin that is gaseous at normal pressure as a raw material olefin, the pressure of the olefin is usually not less than normal pressure and not more than 10 MPa, preferably not less than 0.5 MPa and not more than 5 MPa.

The temperature of the olefin oligomerization reaction is usually -50°C to 220°C, preferably 0°C to 170°C, more preferably 30°C to 100°C.

The reaction time of the olefin oligomerization reaction is generally appropriately determined according to the reaction apparatus used, and is preferably not less than 1 minute and not more than 20 hours.

Example

Hereinafter, the present invention will be described by way of examples and comparative examples.

<Manufacture of 1-hexene>

(1) Output of 1-hexene and decenes

Using gas chromatography, analysis was performed by a quantitative method based on an internal standard method using the following conditions.

Measuring device: GC-2010 (manufactured by Shimadzu Corporation)

Column: DB-1 60m film thickness 0.25μm inner diameter 0.25mm

Heating mode: keep at 50°C for 10 minutes → heat up to 200°C at 5°C/min → hold for 20 minutes

Gasification chamber temperature: 230°C

Detector temperature: 230°C

Split ratio: 39

Carrier Gas: Helium

Internal standard: n-nonane.

(2) Output of polymer

The reaction solution was poured into a mixed solvent of ethanol and methanol, and the precipitated composition was collected by filtration, dried under reduced pressure at 80° C., and measured for weight to obtain it.

(3) Determination of median diameter and particle size distribution of silica/polymethylaluminoxane, solid polymethylaluminoxane, and modified solid polymethylaluminoxane

The median diameter and particle size distribution of solid polymethylaluminoxane and modified solid polymethylaluminoxane were determined by laser diffraction/scattering method in the following measurement solvent after drying using the following measuring device .

Measuring device: SALD-2200J

Determination solvent: n-hexane.

The particle size distribution index uses the Span value.

Span value=(D90-D10)/D50

(Here, D10, D50, and D90 are the particle diameter values when the cumulative distribution function values of the particle size distribution measured by the above method reach 10%, 50%, and 90%, respectively).

(4) Aluminum content of solid polymethylaluminoxane and modified solid polymethylaluminoxane

The aluminum content of the solid polymethylaluminoxane and the modified solid polymethylaluminoxane was measured in the following manner. First, solid polymethylaluminoxane or modified solid polymethylaluminoxane is added to pure water under a nitrogen atmosphere, which is taken out into air and heated to completely evaporate water. After adding sodium carbonate to the precipitated solid, it was heated to melt, and the aluminum content was determined by the ICP-AES method using Vista-PRO manufactured by Varian.

(5) The method for obtaining m/(m+n) in the general formula (1)

The value of m/(m+n) is calculated in the following manner. In the production of modified solid polymethylaluminoxane, when a halogenated alcohol or a halogenated phenol is added to the solid polymethylaluminoxane as a raw material, the reacted halogenated alcohol or halogenated phenol is produced. Equimolar amounts of methane. With this in mind, the aluminum content of the solid polymethylaluminoxane is reported as Xwt%, the aluminum content of the modified solid polymethylaluminoxane as Ywt%, and the molecular weight of the halohydrin or halophenol When expressed as M, Y can be expressed as follows using X, M, and m/(m+n).

.

Therefore, the value of m/(m+n) is obtained by the following formula.

.

(6) Activity of catalyst for olefin oligomerization reaction

As an indicator of catalyst activity, the value obtained by dividing the weight of 1-hexene obtained by the reaction by the amount of the complex used (t/mol complex), and the 1-hexene obtained by the reaction The value obtained by dividing the weight of alkene by the weight of the cocatalyst (silica/polymethylaluminoxane, solid polymethylaluminoxane, or modified solid polymethylaluminoxane) used ( g/g cocatalyst).

(7) Synthesis of known transition metal complexes

Titanium complexes of the following formulas (8) and (9) (hereinafter respectively referred to as "complex 1" and "complex 2") were synthesized according to a known method (Japanese Patent Laid-Open No. 2011-98954), and , a titanium complex of the following formula (10) (hereinafter referred to as "complex 3") was synthesized according to a known method (International Publication No. 2009/005003).

.

(8) Synthesis of known ligands

N,N'-bis(diphenylphosphino)isopropylamine was synthesized according to a known method (A.Bollmann, et al. J. Am. Chem.Soc. 2004, 126, 14712.).

[Reference example 1]

1 g of silica gel (Sylopol 948 manufactured by GRACE-Davison; median diameter=55 μm) dried under a nitrogen atmosphere at 300° C. for 5 hours was weighed into a 200 mL flask, and 15 mL of dehydrated toluene was added thereto. After cooling to 0° C. in an ice bath, a toluene solution of polymethylaluminoxane (Tosoh. Fainchem Co., Ltd.) 5.0 mL (17.5 mmol). After the dropwise addition, the temperature was raised to 95° C., followed by stirring for 4 hours. After the reaction was completed, it was cooled to room temperature, and the supernatant was removed by decantation. Further, 15 mL of toluene was added thereto, stirred, and then left to stand, and the supernatant was removed by decantation again. This washing operation was carried out three times, and finally the silica/polymethylaluminoxane of interest was obtained by drying under reduced pressure at 100° C. for 1 hour. The yield was 1.2 g, and as a result of elemental analysis (weight %), Si: 24% and Al: 19%.

[Reference example 2]

Into a flask replaced with argon, 95.3 g of silica gel (Sylopol 948 manufactured by GRACE-Davison; median diameter = 55 μm;) dried under nitrogen atmosphere at 300° C. for 5 hours was weighed, and toluene was added. 550mL, cooled with ice water. Under ice-water cooling, a toluene solution of polymethylaluminoxane having an aluminum concentration of 3.4 mmol/mL (manufactured by Tosoh Finechem Co., Ltd.) contained in the toluene solution was added dropwise over 1 hour, and stirred for 1 hour under ice-water cooling. After 1 hour, the temperature was raised to 50° C. and stirred for 4 hours. Thereafter, the supernatant was removed, washed twice with 500 mL of toluene and once with 500 mL of hexane, and dried under reduced pressure to obtain 140.1 g of silica/polymethylaluminoxane.

[Reference example 3]

To a 100 mL two-necked flask heated and dried at 110° C. for 30 minutes or more, solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd., aluminum atom = 39.3% by weight, median diameter 17 μm, span value = 1.4 ) 0.81 g and 20 mL of toluene to prepare a slurry, stirred at room temperature, added a solution obtained by dissolving 0.433 g of pentafluorophenol in 1.5 mL of toluene, and stirred for 3 hours. After filtration and separation using a glass filter, the resulting solid was washed twice with 20 mL of toluene, once with 20 mL of hexane, and dried under reduced pressure for 1 hour to obtain a modified solid polymethylaluminum in the form of a white powder. Oxane 1.11 g (median diameter 7 μm, span value=1.5). As a result of elemental analysis, the aluminum content was 26 wt%, and the value of m/(m+n) in the general formula (1) was 0.21.

[Reference example 4~8]

The modified solid polymethylaluminoxane was prepared in the same manner by changing the amount of solid polymethylaluminoxane and pentafluorophenol used in Reference Example 3. Table 1 shows the amount of raw materials used and the results.

[Table 1]

[Reference example 9]

Solid polymethylaluminoxane was prepared according to a known method (Japanese Patent Laid-Open No. 2000-95810). Using the obtained solid polymethylaluminoxane 0.45g and pentafluorophenol 0.61g, by the same method as Reference Example 3, 0.85g of modified solid polymethylaluminoxane (median diameter 64 μm, Span value = 2.0).

[Reference example 10]

To a 20 mL Schlenk tube whose interior was replaced with nitrogen, 95 mg of complex 1, 8 mL of toluene, and 112 μL of triethylamine were added. Next, a solution obtained by dissolving 46 mg of phenol in 2 mL of toluene was added thereto, and stirred at room temperature for 16 hours. The generated precipitate was removed by filtration under a nitrogen atmosphere, and the solvent and remaining triethylamine were distilled off under reduced pressure. Extract the product from the resulting solid with 3 mL of hexane, concentrate it to 1 mL under reduced pressure, and stand overnight at -20°C to obtain the titanium complex shown in Formula 11 in crystal form (hereinafter referred to as "Complex 4") 97 mg.

.

[Example 1]

Into a 5-liter autoclave with a stirrer replaced with argon after drying under reduced pressure, 1600 mL of heptane was charged, the temperature in the system was raised to 40° C., and ethylene was introduced so that the partial pressure reached 3.0 MPa. Make the temperature and pressure in the system stable. Next, 1.0 mL of a hexane solution of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) having a concentration of 1.0 mmol/mL of triisobutylaluminum was added. A slurry obtained by contacting 2 mL of heptane, 34 mg of the modified solid polymethylaluminoxane obtained in Reference Example 3, and 0.2 mL of a toluene solution (5 μmol/mL) of complex 2 at room temperature for 1 minute was put thereinto. material. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 5 hours. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 222 g of 1-hexene (222 t/mol complex, 6530 g/g cocatalyst), 12.5 g of decenes, and 4.2 g of polymer were obtained. Adhesion of an amorphous polymer to a stirring blade or the like was not found.

[Example 2]

Into a 5-liter autoclave with a stirrer replaced with argon after drying under reduced pressure, 1600 mL of heptane was charged, the temperature in the system was raised to 40° C., and ethylene was introduced so that the partial pressure reached 2.0 MPa. Make the temperature and pressure in the system stable. Next, 1.0 mL of a hexane solution of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) having a concentration of 1.0 mmol/mL of triisobutylaluminum was added. A slurry obtained by contacting 2 mL of heptane, 63 mg of the modified solid polymethylaluminoxane obtained in Reference Example 3, and 0.4 mL of a toluene solution (5 μmol/mL) of complex 2 at room temperature for 1 minute was put thereinto. material. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 5 hours. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 294 g of 1-hexene (147 t/mol complex, 4670 g/g co-catalyst), 34.7 g of decenes, and 4.7 g of polymer were obtained. Adhesion of an amorphous polymer to a stirring blade or the like was not found.

[Comparative example 1]

Into a 5-liter autoclave with a stirrer replaced with argon after drying under reduced pressure, 1200 mL of heptane was charged, and polymethylaluminoxane (North Korea) containing an aluminum concentration of 3.4 mmol/mL contained in a toluene solution was charged. 1.8 mL of a toluene solution (manufactured by So Fine Chemical Co., Ltd.). The temperature in the system was raised to 40° C., and ethylene was introduced so that the partial pressure thereof reached 2.0 MPa to stabilize the temperature and pressure in the system. Into this, 0.29 mL of a toluene solution of polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) with an aluminum concentration of 3.4 mmol/mL contained in the toluene solution and a toluene solution of complex 2 (5 μmol/mL ) 0.4mL of the mixture. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 90 minutes. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 184 g of 1-hexene (92 t/mol complex), 23 g of decenes, and 1.0 g of polymer were obtained. Amorphous polymers were found to be attached to stirring blades and the like.

[Comparative example 2]

In a 5-liter autoclave with a stirrer replaced with argon after drying under reduced pressure, 800 mL of heptane was added, and a hexane solution of triisobutylaluminum with a concentration of 1.0 mmol/mL of triisobutylaluminum was added. (manufactured by Tosoh Finechem Co., Ltd.) 1.5 mL. The temperature in the system was raised to 40° C., and ethylene was introduced so that the partial pressure thereof reached 2.0 MPa to stabilize the temperature and pressure in the system. Into this, 0.29 mL of a toluene solution of polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) with an aluminum concentration of 3.4 mmol/mL contained in the toluene solution and a toluene solution of complex 2 (5 μmol/mL ) 0.4mL of the mixture. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 60 minutes. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 18 g of 1-hexene (9 t/mol complex), 0.05 g of decenes, and 0.7 g of polymer were obtained. Amorphous polymers were found to be attached to stirring blades and the like.

[Comparative example 3]

Under a nitrogen atmosphere, 5 mL of toluene was added to the flask, 0.2 μmol of complex 1 and 194 mg of silica/polymethylaluminoxane obtained in Reference Example 1 were added, and stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a solid.

Into a 0.4-liter autoclave with a stirrer, which was dried under reduced pressure and replaced with nitrogen, 90 mL of toluene and a hexane solution of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) with a concentration of 0.93 mmol/mL were put into 2.2 mL, after raising the temperature in the system to 40°C, introduce ethylene up to 2.0 MPa to stabilize the temperature and pressure in the system. 106 mg of the solid obtained above was added thereto. Ethylene gas was continuously supplied to keep the total pressure constant, and the reaction was carried out at 40°C for 60 minutes, and 2.0 mL of ethanol was injected to terminate the reaction. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 7.6 g of 1-hexene (38 t/mol complex, 72 g/g cocatalyst) and 0.5 g of polymer were obtained. Adhesion of an amorphous polymer to a stirring blade or the like was not found.

[Comparative example 4]

Into a 5-liter autoclave with a stirrer that was replaced with argon after drying under reduced pressure, 1600 mL of heptane and a hexane solution of triisobutylaluminum at a concentration of 1.0 mmol/mL (manufactured by Tosoh Finechem Co., Ltd.) were added. ) 1.0 mL, the temperature in the system was raised to 40°C, and ethylene was introduced in such a way that the partial pressure reached 2.0 MPa to stabilize the temperature and pressure in the system. Into this, 4.0 mL of heptane, 294 mg of solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd., aluminum atom = 39.3% by weight), and 0.8 mL of a toluene solution (5 μmol/mL) of complex 2 were added. mixture. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 120 minutes. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 231 g of 1-hexene (58 t/mol complex, 785 g/g cocatalyst), 18.3 g of decenes, and 3.5 g of polymer were obtained. Amorphous polymers were found to be attached to stirring blades and the like.

[Comparative Example 5]

Into a 5-liter autoclave with a stirrer that was replaced with argon after drying under reduced pressure, 1600 mL of heptane and a hexane solution of triisobutylaluminum at a concentration of 1.0 mmol/mL (manufactured by Tosoh Finechem Co., Ltd.) were added. ) 1.0 mL, the temperature in the system was raised to 40°C, and ethylene was introduced in such a way that the partial pressure reached 2.0 MPa to stabilize the temperature and pressure in the system. Into this, 4.0 mL of heptane, 282 mg of solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd., aluminum atom = 39.3% by weight), and 0.8 mL of a toluene solution (5 μmol/mL) of complex 1 were added. mixture. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 120 minutes. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 230 g of 1-hexene (57 t/mol complex, 815 g/g cocatalyst), 18.3 g of decenes, and 3.6 g of polymer were obtained. Amorphous polymers were not found to adhere to stirring blades and the like.

[Example 3]

Into a 0.4-liter autoclave with a stirrer replaced with argon after drying under reduced pressure, 120 mL of heptane was charged, the temperature in the system was raised to 40° C., and ethylene was introduced so that the partial pressure reached 2.0 MPa. Make the temperature and pressure in the system stable. Next, 0.40 mL of a hexane solution (manufactured by Tosoh Finechem Co., Ltd.) having a trioctylaluminum concentration of 1.01 mmol/mL was added. Into this, a slurry obtained by stirring 3 mL of toluene, 33 mg of the modified solid polymethylaluminoxane obtained in Reference Example 3, and 1.0 mL of a toluene solution (1 μmol/mL) of complex 3 at room temperature for 1 hour was added. material. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 60 minutes. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 24 g of 1-hexene (24 t/mol complex, 727 g/g co-catalyst) and 1.5 g of polymer were obtained. Adhesion of an amorphous polymer to a stirring blade or the like was not found.

[Comparative Example 6]

Into a 0.4-liter autoclave with a stirrer replaced with argon after drying under reduced pressure, 120 mL of heptane was charged, the temperature in the system was raised to 40° C., and ethylene was introduced so that the partial pressure reached 2.0 MPa. Make the temperature and pressure in the system stable. Next, 0.40 mL of a hexane solution (manufactured by Tosoh Finechem Co., Ltd.) having a trioctylaluminum concentration of 1.01 mmol/mL was added. Into this, a slurry obtained by stirring 3 mL of toluene, 34 mg of silica/polymethylaluminoxane obtained in Reference Example 2, and 1.0 mL of a toluene solution (1 μmol/mL) of complex 3 at room temperature for 1 hour was added. material. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 60 minutes. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 4.2 g of 1-hexene (4 t/mol complex, 123 g/g co-catalyst) and 0.2 g of polymer were obtained. Adhesion of an amorphous polymer to a stirring blade or the like was not found.

[Comparative Example 7]

Into a 0.4-liter autoclave with a stirrer replaced with argon after drying under reduced pressure, 120 mL of heptane was charged, the temperature in the system was raised to 40° C., and ethylene was introduced so that the partial pressure reached 2.0 MPa. Make the temperature and pressure in the system stable. Next, 0.40 mL of a hexane solution (manufactured by Tosoh Finechem Co., Ltd.) having a trioctylaluminum concentration of 1.01 mmol/mL was added. To this, 3 mL of toluene, 14 mg of solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd., aluminum atom = 39.3% by weight), and 1.0 mL of a toluene solution (1 μmol/mL) of complex 3 were added at room temperature. The resulting slurry was stirred for 1 hour. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 40° C. for 60 minutes. Thereafter, ethylene was emitted, and the content in the autoclave was deashed with ethanol-hydrochloric acid, followed by filtration. 17 g of 1-hexene (17 t/mol complex, 1214 g/g co-catalyst) and 1.5 g of polymer were obtained. Adhesion of an amorphous polymer to a stirring blade or the like was not found.

[Examples 4-16] and [Comparative Examples 8-11]

By the same method as in Examples 1-3 and Comparative Examples 1-7, the ethylene trimerization experiment was carried out by changing the type of complex, the type of alkylaluminum, the type of co-catalyst, the reaction conditions, etc. as described in Table 2. The results of the study are summarized in Table 2.

[Table 2]

[Example 17]

Into a 0.4-liter autoclave with a stirrer replaced with argon after drying under reduced pressure, 120 mL of heptane was charged, the temperature in the system was raised to 45° C., and ethylene was introduced so that the partial pressure reached 3.0 MPa. Make the temperature and pressure in the system stable. Next, 0.24 mL of a toluene solution of trimethylaluminum (2.07 mmol/mL, manufactured by Tosoh Finechem Co., Ltd.) was added. Next, a slurry comprising 2 mL of toluene and 152 mg of the modified solid polymethylaluminoxane obtained in Reference Example 7 was charged. Furthermore, 0.25 mL of a toluene solution (20 μmol/mL) of tris(2,4-pentanedione)chromium (manufactured by Tokyo Chemical Industry Co., Ltd.) and N,N'-bis(diphenylphosphino)isopropyl A toluene solution (27 μmol/mL) of the amine was mixed with 0.25 mL and the mixture was left to stand for 5 minutes to initiate a reaction. Ethylene gas was continuously supplied so as to keep the total pressure constant, and the reaction was carried out at 45° C. for 120 minutes. Thereafter, 1 mL of ethanol was added to terminate the reaction, ethylene was released, and the contents in the autoclave were filtered. The results are shown in Table 3.

[Comparative Example 12]

The experiment was carried out in the same manner as in Example 17 except that 69 mg of solid polymethylaluminoxane was used instead of the modified solid polymethylaluminoxane. The results are shown in Table 3.

[Comparative Example 13]

Instead of the modified solid polymethylaluminoxane, 2.29 mL of a toluene solution of polymethylaluminoxane having an aluminum concentration of 0.44 mmol/mL (manufactured by Tosoh Finechem Co., Ltd.) was used. In the same way, experiment. The results are shown in Table 3.

[table 3]

○: No polymer attachment was found on the reactor and stirring blades;

X: Adhesion of the polymer was observed on the reactor and the stirring blade.

Claims (6)

1. the poly- alkylaluminoxane of modified solid shape of olefin oligomerizationization reaction, a diameter of more than 0.1 μm and 50 μm of its intermediate value are used for Hereinafter, and with the construction unit shown in the construction unit shown in following formulas (a) and following formulas (b),

R' in formula (a) is the alkyl that carbon number is more than 1 and less than 20, and the R'' in formula (b) is that carbon number is 1 Above and less than 20 halogenated alkoxy or haloaryloxy that carbon number is more than 6 and less than 20.

2. the poly- alkylaluminoxane of modified solid shape according to claim 1, wherein, R'' in the formula (b) is former for carbon Subnumber is more than 6 and less than 20 haloaryloxy.

3. the poly- alkylaluminoxane of modified solid shape according to claim 2, wherein, the carbon number is more than 6 and 20 Following haloaryloxy is phenyl-pentafluoride epoxide.

4. the poly- alkylaluminoxane of modified solid shape according to any one of claim 1 to 3, wherein, formula (b) institute Unit number (n) and the formula of the unit number (m) of the construction unit for showing relative to the construction unit shown in the formula (a) B the ratio between total of unit number (m) of construction unit shown in () (m/ (m+n)) is more than 0.05 and less than 0.5.

5. the anti-applications catalyst of olefin oligomerizationization, it contains the poly- alkyl of modified solid shape any one of Claims 1-4 Aikyiaiurnirsoxan beta and the complex compound selected from least a kind in following transition metal complex groups,

Transition metal complex group：Shown in transition metal complex, following formulas (2-2) as shown in following formulas (2-1) The transition metal shown in transition metal complex, following formulas (2-4) shown in transition metal complex, following formulas (2-3) The group of the transition metal complex composition shown in complex compound and following formulas (2-5)；

M in formula (2-1), formula (2-2) and formula (2-3)¹It is the transition metal atoms of the race of the periodic table of elements the 4th；

X in formula (2-1), formula (2-2) and formula (2-3)¹、X²、X³、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹And R in formula (2-2) and formula (2-3)¹²、R¹³、R¹⁴、R¹⁵And R¹⁶And the R in formula (2-3)¹⁷、R¹⁸、R¹⁹、R²⁰And R²¹Respectively From independently be alkyl, carbon number that hydrogen atom, halogen atom, carbon number are more than 1 and less than 20 for more than 1 and 20 with Under substituted alkyl, the alkyl epoxide that carbon number is more than 1 and less than 20, carbon number be more than 1 and less than 20 to take The alkyl epoxide in generation, the silicyl or dibasic amino of substitution；

Selected from R¹、R²、R³And R⁴In both be alkyl that carbon number is more than 1 and less than 20, carbon number be more than 1 and 20 Following substituted alkyl, the alkyl epoxide that carbon number is more than 1 and less than 20 or carbon number are more than 1 and less than 20 Substituted alkyl epoxide when, it is described selected from R¹、R²、R³And R⁴In both optionally from it is each substitution base on eliminating hydrogen atom Position bonding；

Selected from R⁵、R⁶、R⁷、R⁸And R⁹In both be alkyl that carbon number is more than 1 and less than 20, carbon number be more than 1 And less than 20 substituted alkyl, the alkyl epoxide that carbon number is more than 1 and less than 20 or carbon number are more than 1 and 20 It is described selected from R during following substituted alkyl epoxide⁵、R⁶、R⁷、R⁸And R⁹In both optionally from it is each substitution base on eliminate The position bonding of hydrogen atom；

Additionally, being selected from R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶In both be alkyl, carbon number that carbon number is more than 1 and less than 20 For more than 1 and less than 20 substituted alkyl, the alkyl epoxide that carbon number is more than 1 and less than 20 or carbon number be 1 with It is described selected from R during upper and less than 20 substituted alkyl epoxide¹²、R¹³、R¹⁴、R¹⁵And R¹⁶In both optionally from each substitution The position bonding of hydrogen atom is eliminated on base；

Selected from R¹⁷、R¹⁸、R¹⁹、R²⁰And R²¹In both be alkyl that carbon number is more than 1 and less than 20, carbon number be 1 with Upper and less than 20 substituted alkyl, the alkyl epoxide that carbon number is more than 1 and less than 20 or carbon number be more than 1 and It is described selected from R during less than 20 substituted alkyl epoxide¹⁷、R¹⁸、R¹⁹、R²⁰And R²¹In both optionally from it is each substitution base on Eliminate the position bonding of hydrogen atom；

R in formula (2-1)¹⁰And the R in formula (2-1) and formula (2-2)¹¹It is more than 1 to be each independently carbon number And less than 20 alkyl epoxide, the substituted alkyl that carbon number is more than 1 and less than 20, carbon number be more than 1 and 20 with Under alkyl epoxide, the substituted alkyl epoxide that carbon number is more than 1 and less than 20, substitution silicyl or two substitutions Amino；

R¹⁰And R¹¹The position bonding of hydrogen atom is optionally being eliminated from each substitution base；

M in formula (2-4)²It is the transition metal atoms of the race of the periodic table of elements the 4th；

A²¹It is oxygen atom, nitrogen-atoms, phosphorus atoms or sulphur atom, Z¹It is connection A²¹With the group of N, A is connected²¹With the most short key of N Number is more than 4 and less than 6, connects A²¹With Z¹Key option be double bond；

R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、X⁴、X⁵And X⁶Be each independently hydrogen atom, halogen atom, carbon number for more than 1 and 20 with Under alkyl, the substituted alkyl that carbon number is more than 1 and less than 20, the alkyl oxygen that carbon number is more than 1 and less than 20 Base, carbon number are more than 1 and less than 20 substituted alkyl epoxide, the silicyl or dibasic amino of substitution；

Selected from R²⁴、R²⁵、R²⁶、R²⁷And R²⁸In both be alkyl that carbon number is more than 1 and less than 20, carbon number be 1 with Upper and less than 20 substituted alkyl, the alkyl epoxide that carbon number is more than 1 and less than 20 or carbon number be more than 1 and It is described selected from R during less than 20 substituted alkyl epoxide²⁴、R²⁵、R²⁶、R²⁷And R²⁸In both optionally from it is each substitution base on Eliminate the position bonding of hydrogen atom；

R²⁹For alkyl that hydrogen atom, halogen atom, carbon number are more than 1 and less than 20, carbon number are more than 1 and less than 20 Substituted alkyl, hydrocarbon that carbon number is more than 1 and less than 20 fork base or substitution that carbon number is more than 1 and less than 20 Hydrocarbon fork base, connect R²⁹With A²¹Key option be double bond；R²⁹Optionally and Z¹Bonding；

M in formula (2-5)²It is the transition metal atoms of the race of the periodic table of elements the 4th；

A²²It is nitrogen-atoms or phosphorus atoms, Z²It is connection A²²With the group of N, A is connected²²With the most short bond number of N for more than 4 and 6 with Under；

R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、X⁴、X⁵And X⁶Be each independently hydrogen atom, halogen atom, carbon number for more than 1 and 20 with Under alkyl, the substituted alkyl that carbon number is more than 1 and less than 20, the alkyl oxygen that carbon number is more than 1 and less than 20 Base, carbon number are more than 1 and less than 20 substituted alkyl epoxide, the silicyl or dibasic amino of substitution；

Selected from R²⁴、R²⁵、R²⁶、R²⁷And R²⁸In both be alkyl that carbon number is more than 1 and less than 20, carbon number be 1 with Upper and less than 20 substituted alkyl, the alkyl epoxide that carbon number is more than 1 and less than 20 or carbon number be more than 1 and It is described selected from R during less than 20 substituted alkyl epoxide²⁴、R²⁵、R²⁶、R²⁷And R²⁸In both optionally from it is each substitution base on Eliminate the position bonding of hydrogen atom；

R³⁰And R³¹For alkyl that hydrogen atom, halogen atom, carbon number are more than 1 and less than 20 or carbon number be more than 1 and Less than 20 substituted alkyl, R³⁰Or R³¹Optionally and Z²Bonding.

The manufacture method of 6.1- hexenes, the anti-applications catalyst of olefin oligomerizationization described in usage right requirement 5,1- is manufactured by ethene Hexene.